Process for preparing fiber-reactive phthalocyanine azo dyes

ABSTRACT

Process for preparing fiber-reactive water-soluble phthalocyanine azo dyes, using the following conversion stages ##STR1## followed by the diazonium coupling of the fiber-reactive group to the pyrazole ring. The novel intermediates are desirable products.

The present invention relates to the preparation of water-solublefiber-reactive phthalocyanine dyes such as those described in GermanPatent No. 1,095,429 and in Japanese patent application Sho-43-72,370published Oct. 9, 1971 under publication No. Sho-46-34,510.

Among the objects of the present invention is the provision of improvedtechniques for preparing phthalocyanine dyes that are water-soluble andfiber-reactive, as well as the provision of novel intermediatestherefor.

The foregoing and additional object of the present invention will bemore fully understood from the following description of several of itsexemplifications.

According to the present invention water-soluble fiber-reactivephthalocyanine dyes are very conveniently produced from phthalocyaninedyes that are not fiber-reactive but whose nuclei contain at least onesulfonyl halide group. This group is converted to ##STR2## and thendiazotized and further converted to ##STR3## which is then cyclized to##STR4## so that a diazonium compound carrying a fiber-reactive groupcan be affixed to the pyrazole ring by a diazonium coupling reaction.

The entire sequence of reactions is readily effected and each reactionstep goes very cleanly with essentially quantitative conversion and nosignificant by-product formation.

In the formula,

R stands for hydrogen or alkyl having up to 6 carbons,

R¹ stands for hydrocarbyl having up to 18 carbons,

R² stands for hydrocarbyl having up to 18 carbons, and

R³ stands for R² and additionally for hydrogen, and

ar stands for a carbocyclic divalent aromatic or aralkyl groupcontaining up to two benzene rings and up to 16 carbons, a benzene ringcarrying the hydrazone nitrogens.

Phthalocyanine hydroazones containing at least one group of the formulaII represent novel intermediates having not yet been described.

As mentioned above, they are readily obtained by diazotizing aphthalocyanine containing a corresponding number of sulfonylamide groupsof formula I and coupling the diazotized material with a keto-succinicacid ester ##STR5## in which R⁴ is hydrogen, hydrocarbyl having up to 10carbons and alkoxycarbonyl having 2 to 6 carbons and

R¹ and R² are as defined above.

The group R⁴ of the aryl-succinic acid ester is split off together withthe bridging --CO-group by coupling the diazotized sulfonylamides withthe aryl-succinic acid ester.

The diazotization of the sulfonylamides I can be effected in knownmanner in an aqueous acid medium by reaction with nitrous acid or anagent which splits off nitrous acid. A salt of nitrous acid, especiallyan alkali metal salt, such as sodium or potassium nitrite, is generallyemployed in a mineral acid medium as an agent which splits off nitrousacid. In a preferred embodiment, the neutral aqueous solution of thesulfonylamide is treated with a solution of a stoichiometric amount ofsodium nitrite and this mixture is then run, while stirring, into atleast 2.5 moles, preferably 3 moles, of dilute, approximately 5-15%strength hydrochloric acid per mole of amino group present, attemperatures between -5° and +25° C., preferably -2° to +5° C. The diazosuspension thus obtained is then reacted with the succinic acidderivative of the formula IV at a pH between 3 and 8, preferably between4.5 and 5.5, for example by adding the succinic acid derivative to theacid suspension of the diazonium compounds and then adjusting the pHvalue to the desired figure by the addition of alkali, for examplesodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate,potassium carbonate or sodium phosphate.

The aqueous medium in which the coupling of the diazotized amines withthe succinic acid derivatives of formula IV is carried out can alsocontain organic, water-miscible solvents, especially lower aliphaticalcohols, such as for example methanol, ethanol or isopropanol. In thesame way, known coupling accelerators, such as, for example urea orpyridine, can be present during the coupling reaction.

After stirring for 1 to 3 hours unreacted diazotized amine can no longerbe detected and the formation of the hydrazone is complete. It can beseparated out from the solution by salting out, that is to say by addinga neutral, water-soluble salt, such as for example sodium chloride orpotassium chloride.

It is difficult to free the hydrazone from inorganic salts used forsalting out even though it can be done by extraction or dialysis.

The pure hydrazones are stable solids or dark greenish blue color. Onheating up to about 250° they slowly decompose without showing sharpmelting or decomposition points.

In aqueous solution the novel phthalocyanine hydrazones absorb in thevisual region of the electromagnetic spectrum at 620 nm and 655 nm, theshort-wave band having an extinction value being about 10% higher thanthat of the long-wave band. The absolute extinction values are dependenton the molecular weight of the hydrazone measured and, if thesalt-containing products are measured, on the salt content.

For analytical purposes it is not necessary to remove any salt from theproducts salted out and it is not even necessary to separate thehydrazones from aqueous solutions. For the purpose of gravimetricanalysis of the compounds it is of advantage to use a salt-containingproduct and draw all analytical values to the analytical value of thecentral heavy-metal atom of the phthalocyanine nucleus. Qualitativedetermination of the hydrazones in solutions may easily be performed byevaluating the visual spectrum of the solutions along the lines givenabove.

Quantitative determination of the hydrazone content in aqueous solutionsmay be easily made by adding alkali to the solution to obtain a slightlyalkaline pH value, by stirring the solution for 5 to 10 minutes, and bysubsequent titration of the equivalent of phthalocyanine pyrazolone thusobtained by means of a standardized solution of p-nitrophenyldiazoniumchloride, using paper impregnated with a R-salt solution asindicator for excess diazonium compound, i.e. for the determination ofthe end-point. Separation of the hydrazone is, however, in no waynecessary for the further processing of the hydrazones according to theinvention; on the other hand, it is appropriate and advantageous toemploy the reaction solutions obtained in the coupling reaction directlyfor further processing.

The hydrazones of the present invention are valuable intermediateproducts for the manufacture of the desired fiberreactive phthalocyaninedyes. Their conversion to the final dye is very easily effected in veryhigh yields with no significant by-product problems.

In general the ar group of the formulas I, II and III can be

m-phenylene

p-phenylene ##STR6## where n is an integer from 1 through 101,3-naphthylene

1,4-naphthylene

1,5-naphthylene

1,8-naphthylene

2,6-naphthylene

2,7-naphthylene ##STR7## where m is an integer from 1 through 6 and theright-hand slash line represents a bond located at any unsubstitutedlocation in either ring ##STR8## where p is an integer from 1 through 4##STR9## where q and r are each 1 through 3 and

q+r totals no more than 4

and the following additional groups which the art considers to bearomatic in nature ##STR10## and alkylene-linked modifications of these.Preferred are the phenylenes, the naphthylenes, ##STR11## As noted abovethe ar has an aromatic carbon bonded to the the nitrogen that is to bediazotized. Such benzene ring can be fused to another ring or it can beunfused.

The aromatic rings of the above divalent groups standing for ar may befurther substituted.

Appropriately, they contain at least one sulpho group or carboxyl group,but valuable hydrazones according to the invention can also be obtainedwith radicals which have the general definition or ar and which containno acid group. In addition, the hydrocarbon radical can be substitutedin each nucleus by one substituent of the group --OH, alkoxy having 1 to4 C atoms --CN, --CF₃ or --SO₂ R⁵ or an additional --SO₃ H group, or byone or two identical or different substituents of the groups halogen,##STR12## or --COOH. If ar is derived from a phenylene radical, it canbe substituted, additionally to a --SO₃ H group which may perhaps bepresent, by one to three identical or different alkyl radicals having 1to 4 C atoms. Phthalocyanine hydrazones, according to the invention, inwhich ar is phenylene or phenylene substituted by one or two carboxylgroups or by one or two sulpho groups or a naphthylene radical which issubstituted by one or two sulpho groups or a stilbenyl radical which issubstituted by two sulpho groups, and especially these hydrazones inwhich ar is a radical of the formula ##STR13## wherein the positionshown here corresponds to the position in the general formula I, areparticularly preferred.

Hydrocarbyl groups standing for R are methyl, carboxymethyl,sulphomethyl or alkyl radicals which contain 2-6 C atoms and areoptionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms,alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 Catoms, --COOH or SO₃ H.

Preferably, R denotes hydrogen, methyl, carboxymethyl, sulphomethyl oran ethyl radical which is optionally substituted by Cl, OH, alkoxyhaving 1 to 2 C atoms, --COOH or SO₃ H, and particularly denoteshydrogen or methyl.

The hydrocarbyl group standing for R¹ is an alkyl radical which has 2-6C atoms and is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms,or an unsubstituted alkyl radical having 1-18 C atoms, preferably anethyl radical which is substituted by Cl, OH or alkoxy having 1-2 Catoms or an unsubstituted alkyl radical having 1-6 C atoms.

The hydrocarbyl R² occurring in formula II denotes an alkyl radicalwhich has 2-6 C atoms and is substituted by Cl, Br, OH or alkoxy having1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 Catoms and preferably an ethyl radical which is substituted by Cl, OH oralkoxy having 1-2 C atoms, or denotes an unsubstituted alkyl radicalhaving 1-6 C atoms.

Phthalocyanine hydrazones, according to the invention, in which R¹ andR² are identical and denote methyl or ethyl, are particularlyadvantageous.

R³ has the same meanings as R² but may additionally denote hydrogen.

Hydrocarbyl groups standing for R⁴ are alkyl radicals which have 1-10 Catoms and are optionally substituted by alkoxy having 1-4 C atoms oralkoxycarbonyl having 2-6 C atoms, a phenyl radical which is optionallysubstituted by Cl, Br, alkyl or alkoxy having 1-4 C atoms, oralkoxycarbonyl having 2-6 C atoms, preferably, R⁴ denotes alkyl having1-4 C atoms, phenyl, methylphenyl or alkoxycarbonyl having 2 to 3 Catoms. The methyl group is particularly preferred for R⁴.

R⁵ occurring in the substituent --SO₂ R⁵ of the ar group denotes methyl,carboxymethyl, sulphomethyl, alkyl which has 2 or 3 C atoms and isoptionally substituted by Cl, OH, alkoxy having 1-3 C atoms,acetylamino, acetoxy, --COOH or --SO₃ H, benzyl or phenyl, it beingpossible for the aromatic nuclei to be mono-substituted or disubstitutedby --COOH or --SO₃ H, preferably, it denotes methyl and ethyl.

In the substituent ##STR14## of the ar group

R⁶ denotes hydrogen, methyl, carboxymethyl, sulfomethyl, an alkylradical which has 2-6 C atoms and which is optionally substituted by Cl,Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms,preferably acetylamino, benzoylamino, alkanoyloxy having 1-6 C atoms,preferably acetoxy, --COOH or --SO₃ H, a phenalkyl or naphthalkylradical having 1-3 C atoms in the aliphatic chain, or phenyl ornaphthyl, it being possible for the aromatic nuclei to be substituted byCl, Br, OH, alkyl and/or alkoxy having 1-6 C atoms, alkanoylamino having1-6 C atoms, --COOH or --SO₃ H and R⁷ denotes hydrogen, methyl,carboxymethyl, sulphomethyl, an alkyl radical which contains 2-6 C atomsand which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 Catoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxyhaving 1-6 C atoms, --COOH or --SO₃ H, or an unsubstituted alkyl radicalhaving 6-20 C atoms.

Preferably

R⁶ denotes hydrogen, an alkyl radical which contains 2 or 3 C atoms andis optionally substituted by OH, alkoxy having 1-3 C atoms, --COOH orSO₃ H, methyl, carboxymethyl or sulphomethyl, and

R⁷ denotes an alkyl radical which has 2 or 3 C atoms and which isoptionally substituted by OH, alkoxy having 1-3 C atoms, --COOH or --SO₃H, or denotes an unsubstituted alkyl radical having 1-20 C atoms, butespecially denotes hydrogen, methyl, carboxymethyl or an alkyl radicalwhich has 2 or 3 C atoms and which is optionally substituted by OH.

Particularly preferred meanings for R⁶ and R⁷ are hydrogen, alkyl having1 to 4 carbons and β-hydroxyethyl.

The phthalocyanine amides having at least one group of the formula I areprepared by condensation of phthalocyanine sulfochlorides with aromaticor araliphatic diamines of the formula ##STR15## wherein ar has themeaning given above.

If phthalocyanine amides are desired whose group ar bears substituentsas given above, the phthalocyanine sulfochlorides are condensed withdiamines ##STR16## whose group ar bears the desired substituents. Wherethe ar-diamine has an unsymmetrical structure, its condensation to thesulfochloride can be effected by first blocking the amine group that isnot to condense, as by acetylation. After the condensation the blockinggroup is split off to leave a primary amine group that can bediazotized. The condensation reaction is known per se. It is described,e.g. in DAS 1,769,398 and DAS 1,289,206.

As described in the above named literature references, the reaction ofthe phthalocyanine sulfochloride with the said amines can be carried outas by adding the amine to a concentrated aqueous suspension of thesulfochloride in water or a mixture of water and organic, water-misciblesolvents. The reaction can, however, also be carried out in organicsolvents alone. The temperature of the reaction mixture is preferablykept at 0° to 35° C. and the pH value, which is continously displacedinto the acid range during the reaction is kept between 4 and 10,preferably between 6 and 8, by gradual addition of alkali. Alkalis whichcan be used are the customary substances with an alkaline reaction, suchas sodium hydroxide solution, sodium carbonate, potassium carbonate ortrisodium phosphate, Sodium hydroxide solution is preferred. It isadvantageous to add a tertiary amine, such as, for example, pyridine, incatalytic quantities in order to accelerate the reaction.

It is possible to process further the sulfonyl amides of formula I inthe aqueous solution in which they are produced, but it is advantageousto isolate them in order to free them from the small amount ofincompletely reacted reactants which are usually present in the motherliquor.

Isolation of the sulfamides may be carried out by acidifying and saltingout in the same manner as is described above for the hydrazones.

The following may be mentioned as examples of diamines ##STR17## whichcan be used as such or in monoacylated form:

p-phenylenediamine, N-methyl-p-phenylenediamine,N-carboxymethyl-p-phenylenediamine, m-phenylenediamineN-β-hydroxyethyl-m-phenylenediamine, 1,4-phenylenediamine-2-sulphonicacid, 1-amino-4-N-sulphomethylamino-phenylene-2-sulphonic acid,1,4-phenylenediamine-2,5- or 2,6-disulphonic acid,1-amino-4-N-methylamino-phenylene-2,6-disulphonic acid,1,3-phenylenediamine-4-sulphonic acid,1,3-phenylenediamine-4,6-disulphonic acid, 2,4-diamino-toluene-5- or-6-sulphonic acid, 2,6-diamino-toluene-4-sulphonic acid,2,5-diamino-1,3,5-trimethylbenzene-4-sulphonic acid,2,6-diamino-1,3-diethylbenzene-4-sulphonic acid,2,4-diamino-1-chlorobenzene-6-sulphonic acid,2,4-diamino-1-tert.-butyl-benzene-6-sulphonic acid,2,4-diaminotoluene-5- or -6-sulphamide, 2,6-diamino-toluene4-ethanol-sulphamide or 2,6-diaminotoluene-diethanolsulphamide,1,4-diaminophenylene-2-dimethylsuphamide,1,3-diaminophenylene-4-sulphanilide,1,3-diaminophenylene-4-β-hydroxyethylsulphone,N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine,N-butyl-p-phenylenediamine, N-pentyl-p-phenylenediamine,N-hexyl-p-phenylenediamine, N-β-hydroxy-propyl-p-phenylenediamine,N-β-carboxy-propyl-p-phenylenediamine,N-γ-chlorobutyl-p-phenylenediamine,N-δ-methoxy-butyl-p-phenylenediamine,N-δ-propoxy-butyl-p-phenylenediamine,N-β-acetylamino-ethyl-p-phenylenediamine,N-β-butyrylamino-ethyl-p-phenylenediamine,N-benzoylamino-ethyl-p-phenylenediamine,1-N-methyl-3-aminobenzene-4-sulphonic acid,1-N-butyl-4-amino-benzene-3-sulphonic acid,2,4-diamino-phenol-6-sulphonic acid,2,4-diamino-1-methoxybenzene-5-sulphonic acid, 1,5-diaminonaphthalene,1,5-diaminonaphthalene-3-sulphonic acid,1,5-diaminonaphthalene-4-sulphonic acid,1,5-diaminonaphthalene-2-sulphonic acid,1,6-diaminonaphthalene-4-sulphonic acid,1,4-diaminonaphthalene-2-sulphonic acid,1,4-diaminonaphthalene-5-sulphonic acid,1,4-diaminonaphthalene-7-sulphonic acid,1,8-diaminonaphthalene-4-sulphonic acid,2,6-diaminonaphthalene-8-sulphonic acid,2,6-diaminonaphthalene-4,8-disulphonic acid,1,5-diaminonaphthalene-3,7-disulphonic acid,1,4-diaminonaphthalene-5-carboxylic acid,1,4-diaminonaphthalene-2-carboxylic acid,1,8-diaminonaphthalene-3-carboxylic acid, 4,4'-diaminodiphenyl,2,2'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl,4,4'-diaminodiphenyl-2,2'-disulphonic acid, 3,3'-dimethoxy-4,4'-diaminodiphenyl, 1-amino-4-aminomethyl-benzene,1-amino-4-aminomethyl-benzene-3-sulphonic acid,1-amino-4-β-aminoethyl-benzene-2-sulphonic acid,1-amino-4-γ-aminopropyl-benzene-3-sulphonic acid,2-amino-5-aminomethyl-naphthalene-1-sulphonic acid,4,4'-diaminodiphenylmethane-2,2'-disulphonic acid,4,4'-diamino-diphenylethane-2,2'-disulphonic acid,4,4'-diamino-diphenylethanemono-sulphamide,4,4'-diamino-diphenylethane-disulphamide,4,4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diaminodiphenylmethane,4,4'-diamino-diphenylethane-di-β-hydroxyethylsulphamide,4,4'-diamino-diphenylamine-3-sulphonic acid,3,4'-diamino-6-methoxy-diphenylamine-2'-sulphonic acid,3,4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid,3,3'-diaminobenzophenone-5,5'-disulphonic acid,3,4'-diaminobenzophenone-3'-sulphonic acid, 4,4'-diamino-diphenylsulphone, 4,4'-dichloro-3,3'-diamino-diphenyl sulphone,3,3'-diamino-4-methyldiphenyl-sulphone-5-sulphonic acid and3,3'-diamino-diphenylsulphone-4,4'-disulphonic acid.

The aryl succinic acid esters IV are well-known prior art compounds, andare described for instance in U.S. Pat. No. 3,786,083 and in "OrganicSyntheses" XIV (1934), p. 38.

Preferred succinic acid derivatives are those in which R² denotes analkyl radical with 2-6, preferably 2, carbons and which is substitutedby Cl, OH or alkoxy with 1-4, preferably 1-2, carbons, or anunsubstituted alkyl radical with 1-18, preferably 1-6, carbons, R¹denotes an ethyl radical which is substituted by Cl, OH or alkoxy with1-2 carbons or an unsubstituted alkyl radical with 1-6 carbons, and R⁴denotes hydrogen, alkyl with 1-4 carbons, phenyl, methylphenyl oralkoxycarbonyl with 2 or 3 carbons.

Succinic acid derivatives in which R¹ and R² are identical and denotemethyl or ethyl, and R⁴ represents a methyl group, are particularlypreferred.

The phthalocyanine sulfohalides used as starting material for theprocess of the present invention have the --SO₃ hal group preferably inthe 3-position of the phthalocyanine nucleus, the 3-position being on abenzene ring ortho to the isoindole ring to which the benzene ring isfused. However 4-sulfonylhalide-substituted phthalocyanines can also beused for the present invention, as can phthalocyanines containing two,three or four sulfonylhalide groups of either or both kinds. Suchsulfonylhalides are also generally called "sulfohalides".

The phthalocyanine sulfohalides are well known compounds, produced byknown processes. Those sulfohalides having the --SO₂ hal group in3-position are produced by reacting the phthalocyanine with halosulfonicacid HSO₃ hal, sulfohalides having the --SO₃ hal groups in 4-positionare produced by reacting phthalocyanine-4-sulfonic acids withhalosulfonic acid, thionylhalide or phosphorus halide under conditionsdescribed in more detail e.g. in "Venkataraman, The Chemistry ofSynthetic Dyes", Vol. V, p. 261 (1971).

Phthalocyanine-4-sulfonic acids can be prepared by condensation of4-sulfophthalimides as described, e.g. in "Venkataraman, The Chemistryof Synthetic Dyes", Vol. V, p. 260, (1971).

Both methods caan be combined to obtain mixed sulfonylhalides.

Preferred as starting material for the process of the present inventionare those in which the sulfonylhalide group is a sulfonylchloride group--SO₂ Cl.

Al least one --SO₂ Cl group of the starting material has to be condensedwith the ar diamine as described above. If more than one --SO₂ Cl groupis present in the phthalocyanine sulfochloride all these groups may becondensed with the ar diamine but it is also possible to partially reactthem with a monoamine of the formula

    H-NR.sup.6 R.sup.6

which results in the formation of --SO₂ -NR⁶ R⁷ groups linked to thephthalocyanine nucleus. Hence, a poly-sulfochlorided phthalocyanine dyenucleus can be simultaneously reacted with the ar-diamine and with theappropriate monoamine HNR⁶ R⁷. Also a mixture of ar-diamines can besimultaneously reacted with a mono- or poly-sulfochlorided nucleus, withor without such monoamine.

The symbols R⁶ and R⁷ denote radicals selected from the group givenabove for R⁶ and R⁷ of the --SO₂ NR⁶ R⁷ substituent of ar. The --SO₂--NR⁶ R⁷ substituents of ar and of the phthalocyanine nucleus may beidentical or different.

The following may be mentioned as mono-amines which can be used toprovide the ##STR18## structure:

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine,β-hydroxyethylamine, β-methoxyethylamine, bis-β-hydroxyethylamine,aminoacetic acid, taurine, N-methyltaurine, butylamine, caprylamine,laurylamine, aniline, toluidine, chloroaniline, aniline-o-, -m- orp-sulphonic acid, aniline-o-, -m- or -p-carboxylic acid,N-methylaniline, N-ethylaniline-o-, -m- or -p-sulphonic acid,aniline-ω-methanesulphonic acid, benzylamine,N-β-hydroxyethyl-benzylamine, benzylamine-sulphonic acid andβ-acetylaminoethylamine. Besides the groups ##STR19## and eventually##STR20## the phthalocyanine nucleus may contain sulfo groups which maybe present in the starting material along with the sulfonylhalide groupsor may be obtained by hydrolysis of a sulfonylhalide group.

If the number of ##STR21## groups of the phthalocyanine nucleus isdesignated m, the number of ##STR22## groups 1 and that of sulfo groupsk, then generally the sum of k, l and m is 3 or 4, k being 1, 2 or 3, lbeing 0, 1 or 2 and m 1, 2, 3 or 4.

Preferably, l is 0, k is 2 or 3, m is 1 or 2 and k+m equals 3 or 4.

The cyclization of the hydrazone to give the pyrazole of formula III iscarried out extremely easily as by stirring an aqueous solution of thehydrazone at temperatures between 0° and 100° C., preferably 15° to 30°C., at a pH between 8 and 14, for about 2 to about 20 hours to cause thesplitting off of the alcohol R¹ OH. The cyclization can be combined witha saponification of the group --COOR² to produce a pyrazole having thefree carboxyl group. To achieve this it is only necessary to carry outthe reaction near to the upper limit of the range of pH valuesindicated, for example at pH values from 10 to 14. The cyclization canalso be appropriately carried out on the reaction mixture in which thehydrazones are formed, as by increasing its pH value to 10 to 14 andpermitting the thus alkalized mixture to stand, with or withoutstirring, room temperature being sufficient.

As pointed out above, the coupling of a fiber-reactive group to thepyrazoles of formula III, is known in the art. For such coupling thepyrazoles can be reacted with the diazonium compound of an aminecarrying the desired fiber-reactive group Z, such as ##STR23## whichreadily and cleanly couples to the pyrazolone ring. If desired, thepyrazolone reactant need not be separated from the solution in which itis formed before subjecting it to this coupling reaction. The couplingtakes place at temperatures between -5° and +35° C., preferably +5 to+20° C., and the coupling reaction mixture is subsequently stirred, ifnecessary with cooling, at temperatures between -5° and +25° C.,preferably +5° to +15° C., until the coupling reaction has ended. Duringthe course of the coupling reaction, which generally only takes a fewminutes, the pH value is kept at values from 3 to 8, preferably 5 to 6,by the successive addition of a buffer or an alkali.

Fiber-reactive groups Z are those which contain a radical which can besplit off as an anion or as a neutral radical or contain an activateddouble bond which is capable of addition reactions, and which are thusable of reacting with the hydroxyl groups of cellulose when the dyes areapplied to cellulose materials in the presence of acid-binding agentsand/or under the action of heat, or, when applied to high-molecularweight polyamide fibers, such as wool, reacting with the nucleophiliccenters of these fibers with the formation of covalent bonds. Radicalswhich can be split off by nucleophilic attack are those which, becauseof their position in the periodic system and/or because of a positivecharge center, are strongly electron-attracting. Activated double bondsare, for example, those which are conjugated with a polar double bond,for example a carbonyl group. A large number of fiber-reactive groupingsof this type are known from the literature.

A survey of this subject is given in "K. Venkataraman The Chemistry ofSynthetic Dyes", Vol. VI, pages 4 to 182, Academic Press (1972).

Examples of specific groups suitable to stand for Z in the dyestuffs ofthe present invention and described in greater detail in the above citedliterature are radicals of α, β-unsaturated acids, radicals of acidswhich contain a substituent which can be easily replacednucleophilically, or which gives radicals of α, β-unsaturated acids whena neutral or anionic group is split off, or which contain avinylsulphone or β-halogenoalkyl or β-sulphatoalkylsulphone group,radicals of heterocyclic carboxylic or sulphonic acids which carry asubstituent which is easily replaced during the course of theapplication by the radical of cellulose or by a nucleophilic group ofthe wool or the polyamide, such as, for example, the radicals of2,3-dichloroquinoxaline-5- or -6- sulphonic acid,2,3-dichloroquinoxaline-5- or -6-carboxylic acid, radicals ofsix-membered heterocyclic compounds containing 2 or 3 N atoms, such ass-triazinyl and pyrimidinyl radicals, which carry on at least one of theremaining positions at least one substituent which can be easilynucleophilically replaced.

In cases where the pyrimidine ring or triazine ring only carries onesuch labile substituent, this ring can carry one non-labile substituenton the remaining carbon atom or more non-labile substituents onremaining carbon atoms. A non-labile substituent is to be understood asa group which is bonded to a carbon atom of the triazine or pyrimidinering by a covalent bond, this covalent bond not being broken open underthe conditions used in applying the reactive dyestuff.

Examples of these non-labile substituents which may be mentioned are theamino group and mono-substituted or di-substituted amino groups andetherified hydroxyl and mercapto groups.

A well-known reactive group having besides one labile substituent onenon-labile substituent is, e.g. the group ##STR24##

A large number of groups of this type are described in the above citedliterature and in patent application, e.g. in German Patent applicationlaid open to public inspection (Offenlegungsschrift)No. 2,152,511 and in"Venkataraman, The Chemistry of Synthetic Dyes", Vol. VI, p. 130-155,(1972).

A further known class of reactive groups derived from this lastmentioned reactive group is characterized in that it has a secondreactive group linked to the non-labile substituent of the firstreactive group. One Example of this type of double-reactive groups hasthe formula ##STR25##

Reactive groups of this type are described in greater detail in Germanpatent application laid open to public inspection(Offenlegungsschrift)Nos. 1,910,044, 2,101,940 and 2,109,879.

In the formula H₂ N-ar¹ -NR⁸ Z the radical ar¹ stands for the same typesof groups as ar, but having the nitrogen to be diazotized carried by abenzene ring, R⁸ denotes hydrogen or alkyl having 1 to 4 carbons.

Typical reactive-group-supplying reactants are:

    __________________________________________________________________________    Typical reactive-group-supplying reactants are:                                                     Z                       X                               __________________________________________________________________________     ##STR26##                                                                                      ##STR27##                                                    ##STR28##                                                                                      ##STR29##                                                    ##STR30##                                                                                      ##STR31##                                                    ##STR32##                                                                                      ##STR33##                                                    ##STR34##                                                                                      ##STR35##                                                    ##STR36##                                                                                      ##STR37##                                                    ##STR38##                                                                                      ##STR39##                                                    ##STR40##                                                                                      ##STR41##                                                    ##STR42##                                                                                      ##STR43##                                                    ##STR44##                                                                                      ##STR45##                                                    ##STR46##                                                                                      ##STR47##                                                    ##STR48##                                                                                      ##STR49##      Cl                                            ##STR50##                                                                                      ##STR51##      Cl                                            ##STR52##                                                                                      ##STR53##      Cl                                            ##STR54##                                                                                      ##STR55##      Cl                                            ##STR56##                                                                                      ##STR57##      Cl                                            ##STR58##                                                                                      ##STR59##      Cl                                            ##STR60##                                                                                      ##STR61##      Cl                                            ##STR62##                                                                                      ##STR63##      Cl                                            ##STR64##                                                                                      ##STR65##      NH.sub.2                                      ##STR66##                                                                                      ##STR67##                                                                                     ##STR68##                                    ##STR69##                                                                                      ##STR70##                                                                                     ##STR71##                                    ##STR72##                                                                                      ##STR73##      OCH.sub.2CH.sub.2OCH.sub.3                    ##STR74##                                                                                      ##STR75##                                                                                     ##STR76##                                    ##STR77##                                                                                      ##STR78##                                                                                     ##STR79##                                    ##STR80##                                                                                      ##STR81##                                                                                     ##STR82##                                    ##STR83##                                                                                      ##STR84##                                                                                     ##STR85##                                    ##STR86##                                                                                      ##STR87##      Cl                                            ##STR88##                                                                                      ##STR89##                                                                                     ##STR90##                                    ##STR91##                                                                                      ##STR92##                                                    ##STR93##                                                                                      ##STR94##                                                    ##STR95##                                                                                      ##STR96##                                                    ##STR97##                                                                                      ##STR98##                                                    ##STR99##                                                                                      ##STR100##                                                                                    ##STR101##                                   ##STR102##                                                                                     ##STR103##                                                                                    ##STR104##                                  __________________________________________________________________________

Diazocomponents of the formula ##STR105## are prepared by known per seprocesses, e.g. by acylating aromatic diamines H₂ N-ar¹ -NHR⁸ withhalides of the formula hal-Z.

A large number of acylating agents of the formula hal-Z can be reactedwith ar¹ -diamines to give the diazotizablefiber-reactive-group-supplying reactant.

The most important ones are: cyanuric chloride and cyanuric bromide,dihalogeno-mono-amino-triazines, it being possible for the amino groupsas the non-reactive substituent to be substituted analogously to theequation described above, such as 2,6-dichloro-4-amino-triazine,2,6-dichloro-4-methylamino-triazine,2,6-dichloro-4-hydroxyethylaminotriazine,2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4-(o-, m- orp-sulphophenyl)-aminotriazine or 2,6-dichloro-4-(2',4'- or2',5'-disulphophenyl)-aminotriazine, dihalogeno-alkoxy-sym.-triazinesand dihalogeno-aryloxy-sym.-triazines, such as2,6-dichloro-4-methoxytriazine, 2,6-dichloro-4-i-propoxytriazine, or2,6-dichloro-4-phenoxytriazine, tetrahalogenopyrimidines, such astetrachloro-, tetrabromo- or tetrafluoro- pyrimidine,2,4,6-trihalogeno-pyrimidines, such as 2,4,6-trichloropyrimidine,2,4,6-tribromopyrimidine or 2,4,6-trifluoropyrimidine,2,4,6-trichloro-5-nitropyrimidine, 2,4,6-trichloro-5-methylpyrimidine,2,4,6-trichloro-5-carbomethoxypyrimidine or2,4,6-trichloro-5-cyanopyrimidine or2,6-difluoro-4-methyl-5-chloropyrimidine,2,4-difluoro-pyrimidine-5-ethylsulphone,2,6-difluoro-4-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine,4,6-difluoro-2,5-dichloropyrimidine or4,6-difluoro-2,5-dibromopyrimidine,2-methylsulphonyl-4-chloro-6-methylpyrimidine,2,6-bis-methylsulphonyl-4,5-dichloropyrimidine,2-methylsulphonyl-4,5-dichloro-6-methylpyrimidine,2-ethylsulphonyl-4,6-dichloropyrimidine, derivatives of heterocycliccarboxylic or sulphonic acids, such as3,6-dichloropyridazine-4-carboxylic acid chloride,2,4-dichloropyrimidine-5-carboxylic acid chloride,2,4,6-trichloropyrimidine-5-carboxylic acid chloride,2-methyl-4-chloropyrimidine-5-carboxylic acid chloride,2-chloro-4-methylpyrimidine-5-carboxylic acid chloride,2,6-dichloropyrimidine-4-carboxylic acid chloride,2-methylsulphonyl-6-chloropyrimidine-4-carboxylic acid chloride or2-methylsulphonyl-6-chloropyrimidine-5-carboxylic acid chloride,2-ethylsulphonyl-6-chloropyrimidine-4-carboxylic acid chloride or2-ethylsulphonyl-6-chloropyrimidine-5-carboxylic acid chloride,2,6-bis-(methylsulphonyl)-pyrimidine-4-carboxylic acid chloride,2-methylsulphonyl-6-methyl-4-chloropyrimidine-5-carboxylic acid chlorideor bromide or 2-methylsulphonyl-6-methyl-4-bromopyrimidine-5-carboxylicacid chloride or bromide,2,6-bis-(methylsulphonyl)-4-chloropyrimidine-5-carboxylic acid chloride,2- or 3-monochloroquinoxaline-6-carboxylic acid chloride or 2- or3-monochloroquinoxaline-6-sulphonic acid chloride, 2- or3-monobromoquinoxaline-6-carboxylic acid bromide or 2- or3-monobromoquinoxaline-6-sulphonic acid bromide,2,3-dichloroquinoxaline-6-carboxylic acid chloride or2,3-dichloroquinoxaline-6-sulphonic acid chloride,2,3-dibromoquinoxaline-6-carboxylic acid bromide or2,3-dibromoquinoxaline-6-sulphonic acid bromide,1,4-dichlorophthalazine-6-carboxylic acid chloride or1,4-dichlorophthalazine-6-sulphonic acid chloride and the correspondingbromine compounds, 2,4-dichloroquinazoline-6-carboxylic acid chloride,2,4-dichloroquinazoline-7-carboxylic acid chloride or2,4-dichloroquinazoline-6-sulphonic acid chloride or2,4-dichloroquinazoline-7-sulphonic acid chloride and the correspondingbromine compounds, N-methyl-N-(2,4-dichlorotriazinyl-6)-aminoacetylchloride, 2-chlorobenzthiazole-5-carboxylic acid chloride or2-chlorobenzthiazole-6-carboxylic acid chloride or2-chlorobenzthiazole-5-sulphonic acid chloride or2-chlorobenzthiazole-6-sulphonic acid chloride and the correspondingbromine compounds, 2-methylsulphonyl- or 2-ethylsulphonyl- or2-phenylsulphonyl-benzthiazole-5-sulphonic acid chloride or2-methylsulphonyl- or 2-ethylsulphonyl- or2-phenylsulphonylbenzthiazole-6-sulphonic acid chloride or aliphaticreactants, such as acrylic acid chloride, mono-, di- ortri-chloroacrylic acid chloride, 3-chloropropionic acid chloride,3-phenylsulphonyl-propionic acid chloride, 3-methylsulphonylpropionicacid chloride, 3-ethylsulphonyl-propionic acid chloride,3-chloroethane-sulphochloride, α-methylsulphonylacrylic acid chlorideand α-bromoacrylic acid chloride.

The acylation by these compounds is carried out in a manner which is initself knwon in an aqueous, aqueous-organic or organic solvent by meansof a Schotten-Baumann reaction at temperatures between 0° and 80° C.,preferably between 10° and 25° C., the acid liberated appropriatelybeing neutralized or buffered off by adding alkali, such as for examplesodium bicarbonate, sodium carbonate, sodium hydroxide solution orsodium acetate. Possible organic solvents are acetone, chlorinatedhydrocarbons, such as ethylene chloride or chlorobenzene, or alsoaprotic polar solvents, such as dimethylformamide.

The preparation of the above mentioned reactive ar¹ diamines isdescribed in greater detail in "Venkataraman, The Chemistry of SyntheticDyes" Vol. VI, pages 211 to 296 (1972) and in several patents andpublications cited therein.

Other known valuable fiber-reactive groups are the vinyl sulfonylgroupand β-substituted ethylsulfonyl groups, whose β-substituent is easy tosplit off together with an alpha hydrogen of the ethyl group in thealkaline pH range.

Very suitable reactive groups of this type are β-chloro-ethylsulfonyl,β-sulfatoethylsulfonyl and β-hydroxyethylsulfonyl; most preferred isβ-sulfatoethylsulfonyl.

This type of reactive groups is described in greater details in"Venkataraman, The Chemistry of Synthetic Dyes", Vol. VI, pages 4 to 85(1972).

This type of reactive groups can be introduced into the phthalocyaninepyrazolone by coupling it with diazotized amines having the formula##STR106## wherein Y is a fibre reactive group of the vinyl sulfonyl orβ-substituted ethylsulfonyl type, ar² stands for the same types ofgroups as ar having the ##STR107## substituent carried by a benzenering, A denotes a group --NH--CO-- or --NH--SO₂ -- and s stands for 0 or1.

Diazotization and coupling of the diazonium compound is carried outunder the same conditions as described above in respect of thediazotization and coupling of amines of the formula ##STR108##

The dyestuff can then be isolated by salting-out, from the aqueoussolutions of the phthalocyanine azo dyestuffs obtained in this way, orit can be obtained in the form of a solid dyestuff preparation byspray-drying the solutions.

The water-soluble, fibre-reactive phthalocyanine dyestuffs which can bemanufactured according to the invention are outstandingly suitable fordyeing and printing cellulose materials, cellulose-containing materialsand natural and synthetic polyamide materials. They are distinguished bya high degree of fixation, particularly in printing processes and infixing by means of dry heat, and by ease of wahing-out the non-fixedportion of dyestuff and they give yellowish-tinged to bluish-tingedgreen dyeings and prints of high brilliance and depth of colour whichhave very good fastness to light, good fastness to wet processing, suchas washing at 60° C. and 95° C., fastness to sea water, fastenss to acidand alkaline perspiration, fastness to chlorinated pool water, fastnessto peroxides and fastness to flue gases.

Mixtures of dyestuffs which can be manufactured according to theinvention, especially those in which the meanings of k and/or l and/or mare different in the individual components, are also outstandinglysuitable for dyeing and printing cellulose materials and display thesame advantageous properties as the individual dyestuffs.

EXAMPLE 1

188 g of m-phenylenediamine-sulphonic acid are dissolved in about 6,000ml of water to give a neutral solution. 190 g of cyanuric chloride,dissolved in acetone, are added to this solution at 0°-5° C. and the pHis simultaneously kept between 6 and 7 with about 100 ml of 10 N sodiumhydroxide solution. When no further m-phenylenediamine-sulphonic acidcan be detected, 70 g of sodium nitrite are added to the neutralsolution and the mixture is then stirred into 250 ml of 10 Nhydrochloric acid at 0°-3° C. When the diazotisation ceases, the diazosuspension is added to a solution ofN-[3-(3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho-phenyl]-Ni-trisulpho-phthalocyaninylsulphonamide,to which 100 g of bicarbonate have previously been added. The couplingceases in a few minutes.

The green phthalocyanine azo dyestuff formed can be isolated by saltingout or spray-drying.

The solution of the phthalocyaninepyrazolone, required for the couplingreaction, can be obtained in the following manner:

1,060 g of3-(3-amino-4-sulpho-phenyl)-amino-sulphonyl-nickel-phthalocyanine-3',3",3"'-trisulphonicacid, manufactured in the customary manner by condensation reaction ofnickel phthalocyanine sulphochloride with 1,3-diaminobenzene-4-sulphonicacid, are stirred with 7,000 ml of water and dissolved by adding 400 mlof 10 N sodium hydroxide solution. 72 g of sodium nitrite are added tothis solution and the mixture is then stirred into a mixture of 2,000 gof ice and 300 ml of concentrated hydrochloric acid in the course of 30minutes. A temperature of 0° to 5° C. is maintained by adding a further2,000 g of ice. After a short time, any possible excess of nitrite isdecomposed by adding aminosulphonic acid. 21 g of acetylsuccinic aciddimethyl ester are poured into the diazo suspension thus obtained. ThepH value is subsequently initially kept at 5.5 by sprinkling inapproximately 13 g of sodium carbonate, and then at 5 to 6 withapproximately 21 g of sodium bicarbonate. The mixture is subsequentlystirred for approximately 1 hour. The end of the reaction can berecognised as being when the pH remains constant and when no change inshade occurs if a solution of H-acid in 2 N sodium carbonate is added toa sample.

350 ml of 10 N hydroxide solution are added to the solution thusobtained of[3-(nickel-trisulpho-phthalocyaninyl-sulphonylamino)]-6-sulpho-phenylhydrazoneof oxalacetic acid dimethyl ester, whereby the pH rises to values of 12to 13. The mixture is stirred for several hours, preferably overnight,at room temperature. The rearrangement to giveN-[3-(3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho-phenyl]-nickel-trisulpho-phthalocyaninyl-sulphonamideis then complete; the pH is adjusted back to 8 with a littlehydrochloric acid and the resulting crude solution is employed direct inthe coupling reaction.

If the cyanuric chloride is replaced by an equi-molar amount of one ofthe acylating agents in the following and the procedure followed isotherwise as described above, valuable green reactive dyes are likewiseobtained:

2,4,6-trisulpho-1,3,5-triazine, β-chloropropionic acid chloride,α,β-dibromopropionic acid chloride, β-phenylsulphonylpropionic acidchloride, β-pyridiniumpropionic acid chloride, β-sulphatopropionic acidchloride, acrylic acid chloride, α-bromoacrylic acid chloride,3-β-chloroethylsulphonylbenzoic acid chloride,4-vinylsulphonylcyclohexanecarboxylic acid chloride,4-β-chloroethylsulphonyl-2,5-endomethylene-cyclohexanecarboxylic acidchloride, ω-(β-chloroethylsulphonyl)-butyric acid chloride,2,4-dichloro-pyrimidine-5-carboxylic acid chloride,2,4-dibromo-pyrimidine-5-carboxylic acid bromide,2,4-difluoro-pyrimidine-5-carboxylic acid chloride,2,6-dichloro-pyrimidine-4-carboxylic acid chloride,2,3-dichloroquinoxaline-6-carboxylic acid chloride,2,3-dichloroquinoxaline-6-sulphonic acid chloride,1,4-dichloro-phthalazine-6-sulphonic acid chloride,1,4-dichloro-phthalazine-6-carboxylic acid chloride,2-methylsulphonyl-6-chloro-pyrimidine-4-carboxylic acid chloride,3,6-dichloro-pyridazine-4-carboxylic acid chloride,2-methylsulphonyl-6-chloro-pyrimidine-5-carboxylic acid chloride and2,6-bis(methylsulphonyl)-pyrimidine-5-carboxylic acid chloride.

If the condensation product of nickel phthalocyanine sulphochloride andone of the following amines is used instead of the similar condensationproduct of Example 1, valuable green reactive dyestuffs are likewiseobtained: 1,4-phenylenediamine-2-sulphonic acid,1,3-phenylenediamine-4,6-disulphonic acid,1,4-phenylenediamine-2,5-disulphonic acid,1,4-phenylenediamine-2,6-disulphonic acid,2,4-diaminotoluene-6-sulphonic acid, 2,6-diaminotoluene-4-sulphonicacid, 2,4-diamino-1,3,5-trimethylbenzene-6-sulphonic acid,2,6-diaminonaphthalene-4,8-disulphonic acid,1,5-diaminonaphthalene-2-sulphonic acid,2,6-diaminonaphthalene-8-sulphonic acid,1-amino-4-aminomethyl-benzene-3-sulphonic acid,2-amino-5-aminomethyl-naphthalene-1-sulphonic acid,4,4'-diamino-diphenylamine-3-sulphonic acid,3,3'-diamino-4-methyl-diphenylsulphone-5-sulphonic acid,1,3-phenylenediamine (acetyl derivative, subsequently saponified),2,4-diaminotoluene (acetyl derivative, subsequently saponified),1,4-phenylenediamine (acetyl derivative, subsequently saponified),4,4'-diamino-diphenylethane-2-2'-disulphonic acid,4,4'-diamino-diphenylethane-mono-sulphamide,4,4'-diamino-diphenylethane-disulphamide,4,4'-diaminostilbene-2-2'-disulphonic acid,4,4'-diamino-diphenylethane-di-β-hydroxyethylsulphamide,4,4'-diamino-diphenylamine-3-sulphonic acid,3,4'-diamino-6-methoxy-diphenylamine-2'-sulphonic acid,3-4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid,3,3'-diaminobenzophenone-5,5'-disulphonic acid,3,4'-diaminobenzophenone-3'-sulphonic acid,4,4'-diamino-diphenylsulphone,4,4'-dichloro-3-3'-diamino-diphenylsulphone,3,3'-diamino-4-methyl-diphenylsulphone-5-sulphonic acid and3,3'-diamino-diphenylsulphonic-4-4'-disulphonic acid.

EXAMPLE 2

268 g of p-phenylenediamine-2,6-disulphonic acid are reacted in thecustomary manner with 183 g of methoxy-dichlorotriazine. After adding 70g of sodium nitrite, the solution of the resulting condensation productis allowed to run into 250 ml of 10 N hydrochloric acid, and the diazosuspension thus obtained is subsequently added, as described in Example1, to a solution of bispyrazolone manufactured as described below from535 g of3,3'-bis-[(4-aminophenyl)-aminosulphonyl]-nickel-phthalocyanine-3",3"'-disulphonicacid. The pH is subsequently adjusted to 7-7.2 with 4 N sodium carbonatesolution and the green dyestuff formed is isolated by salting out orspray-drying.

The bispyrazolone employed as the coupling component was manufactured inthe following manner:

535 g of3,3'-bis/(4-aminophenyl)-amino-sulphonyl)-nickel-phthalocyanine-3",3"'-disulphonicacid, manufactured in the customary manner by condensation of 0.5 mol ofnickel phthalocyanine tetrasulphochloride with 1 mol ofacetyl-p-phenylenediamine and saponification of the condensationproduct, are stirred with 3,500 ml of water and dissolved by adding 200ml of 10 N sodium hydroxide solution. 70 g of sodium nitrite are addedto this solution and the mixture is then stirred into a mixture of 2,000g of ice and 300 ml of concentrated hydrochloric acid in the course ofabout 30 minutes. The temperature is kept between 0° and 5° C. by addinga further 100 g of ice. The mixture is subsequently stirred for about 10minutes and any possible slight excess of nitrite is then removed withaminosulphonic acid. 135 g of acetylsuccinic acid diethyl ester areadded to the diazo suspension thus obtained. The pH is adjusted to about6 with approximately 250 g of sodium carbonate and kept at this valueuntil no further diazo compound can be detected. A solution ofturquoise-coloured3,3'-bis-[4-(1,2-bis-ethoxy-carbonyl-ethylidene)-hydrazino-phenyl-amino-sulphonyl-]nickel-phthalocyanine-3",3"'-disulphonicacid is thus obtained, which is converted direct to the correspondingbispyrazolone by the action of alkali by adding about 400 ml of 10 Nsodium hydroxide solution and stirring the mixture at room temperaturefor approximately 4 hours.

If the corresponding 4,4',4",4"'-derivative is used instead of the amineemployed above, valuable phthalocyanine hydrazones are likewiseobtained.

If the condensation product of nickel phthalocyanine sulphochloride andtwo mols of one of the following ar-diamines is used as the diazocomponent for the pyrazolone step instead of the ar-diamine employedabove and the procedure followed is otherwise as described above, greenphthalocyanine azo dyes are likewise obtained. 1,3-phenylenediamine(acetyl derivative, subsequently saponified), 2,4-diaminotoluene (acetylderivative, subsequently saponified), 2,4-diaminoanisole (acetylderivative, subsequently saponified), 1,4-phenylenediamine-2-sulphonicacid, 2,4-diamino-toluene-6-sulphonic acid, 4-amino-benzylamine(4-acetyl derivative, subsequently saponified),4,4'-diaminostilbenedisulphonic acid, 4,4'-diaminomethanedisulphonicacid or 4,4'-diamino-diphenylamine-3-sulphonic acid.

If the acetylsuccinic acid diethyl ester employed as the couplingcomponent for the pyrazolone step is replaced by one of the followingderivatives of succinic acid, arylhydrazones which can be processedaccording to the invention to give valuable azo phthalocyanine dyes arelikewise obtained.

    ______________________________________                                         ##STR109##                                                                   R.sup.1      R.sup.2       R.sup.3                                            ______________________________________                                        CH.sub.3     CH.sub.3      H                                                  CH.sub.3     C.sub.2 H.sub.4 Cl                                                                          CH.sub.3                                           CH.sub.3                                                                      i-C.sub. 3 H.sub.4                                                                         CH.sub.3                                                         CH.sub.3                                                                      i-C.sub. 4 H.sub.9                                                                         COOCH.sub.3                                                      CH.sub.3                                                                      i-C.sub. 6 H.sub.11                                                                        COOC.sub.2 H.sub.5                                               CH.sub.3     C.sub.2 H.sub.4OH                                                                           CH.sub.3                                           CH.sub.3     C.sub.3 H.sub.6OCH.sub.3                                                                    COOC.sub.3 H.sub.4                                 CH.sub.3     C.sub.2 H.sub.5                                                                             COOC.sub.3 H.sub.4                                 C.sub.3 H.sub.7                                                                            C.sub.2 H.sub.5                                                                             C.sub.3 H.sub.7                                    C.sub.5 H.sub.11                                                                           C.sub.2 H.sub.5                                                                             CH.sub.2C.sub.6 H.sub.5                            C.sub.9 H.sub.19                                                                           C.sub.2 H.sub.5                                                                             COOCH.sub.3                                        C.sub.16 H.sub.33                                                                          C.sub.2 H.sub.5                                                                             C.sub.6 H.sub.5                                     C.sub.2 H.sub.4OC.sub.2 H.sub.5                                                           C.sub.2 H.sub.5                                                                             C.sub.6 H.sub.4CH.sub.3                            ______________________________________                                    

If the methoxydichlorotriazine is replaced by one of the followingreactive components mentioned during the acylation ofp-phenylenediamine-2,6-disulphonic acid, soluble fiber-reactive dyes arelikewise obtained. 2-amino-4,6-dichloro-1,3,5-triazine,2-phenoxy-4,6-dichloro-1,3,5-triazine,2-phenylamino-4,6-dichloro-1,3,5-triazine,2-N-methyl-N-phenylamino-4,6-dichloro-1,3,5-triazine,2-butylmercapto-4,6-dichloro-1,3,5-triazine,2-β-methoxyethoxy-4,6-dichloro-1,3,5-triazine,2-(2'-carboxyphenoxy)-4,6-dichloro-1,3,5-triazine,2-carboxymethylthio-4,6-dichloro-1,3,5-triazine,2-phenylthio-4,6-dichloro-1,3,5-triazine, condensation product of 1 molof cyanuric chloride and 1 mol of2-β-amino-ethylamino-4-(2',5'-disulphophenylamino)-6-chlorotriazine-1,3,5,condensation product of cyanuric chloride and 1 mol of2-4'-amino-3'-sulpho-phenylamino-4-(2"-carboxyphenylamino)-6-chlorotriazine-1,3,5,condensation product of cyanuric chloride and 1 mol of2-3'-amino-4'-sulpho-phenylamino-4-n-butoxy-6-chlorotriazine-1,3,5,2,4-disulpho-6-chloro-1,3,5-triazine, tetrachloropyrimidine,2,4,6-trichloropyrimidine, 5-cyano-2,4,6-trichloropyrimidine,5-nitro-2,4,6-trichloropyrimidine, 2,4-difluoro-6-chloropyrimidine,2-methylsulphonyl-4-methyl-6-chloropyrimidine, condensation product ofcyanuric chloride and2-methoxy-4-β-hydroxyethoxy-6-chloro-1,3,5-triazine,2-methylsulphonyl-4,6-dichloropyrimidine,2,3-dichloroquinoxyline-5-carboxylic acid chloride,2,3-dichloroquinoxyline-6-carboxylic acid chloride,2,3-dichloroquinoxaline-5-sulphonic acid chloride,2,3-dichloroquinoxaline-6-sulphonic acid chloride,2,4-dichloroquinazoline-6-carboxylic acid chloride,2,4-dichloroquinazoline-6-sulphonic acid chloride,2,4-dichloroquinazoline-7-sulphonic acid chloride,1,4-dichlorophthalazine-6-carboxylic acid chloride,3,6-dichloropyridazine-4-carboxylic acid chloride,2,4-dichloropyrimidine-5-carboxylic acid chloride or2,4-difluoropyrimidine-6-carboxylic acid chloride.

EXAMPLE 3

If the sulfonamides in the following table are substituted for thesulfonamide in Example 1, that is to say3-[(3-amino-4-sulpho-phenyl)-amino-sulphonyl-]-nickel-phthalocyanine-3',3",3"'-trisulphonicacid, and the procedure followed is otherwise unchanged, there areobtained valuable hydrazones of oxalacetic acid methyl ester which canbe further processed to correspondingly substituted pyrazoles to makefiber-reactive dyes in accordance with the present invention: ##STR110##where Pc is the phthalocyanine dye nucleus.

    __________________________________________________________________________    R.sup.5   R.sup.6      R          ar          a b c                           __________________________________________________________________________    H         CH.sub.3     H                                                                                         ##STR111## 2 1 1                           H         CH.sub.2COOH H                                                                                         ##STR112## 2 1 1                           H         C.sub.2 H.sub.4SO.sub.3 H                                                                  CH.sub.3                                                                                  ##STR113## 1 1 2                           H         C.sub.2 H.sub.4 Cl                                                                         H                                                                                         ##STR114## 2 1 1                           H         C.sub.2 H.sub.4 OH                                                                         C.sub.2 H.sub.5                                                                           ##STR115## 2 1 1                           H         C.sub.2 H.sub.4OC.sub.2 H.sub.5                                                            C.sub.2 H.sub.5                                                                           ##STR116## 2 1 1                           H         C.sub.4 H.sub.8NHCOCH.sub.3                                                                H                                                                                         ##STR117## 2 1 1                           H         C.sub.6 H.sub.10NHCOC.sub.6 H.sub.6                                                        H                                                                                         ##STR118## 2 1 1                           H         C.sub.2 H.sub.4SO.sub.3 H                                                                  C.sub.2 H.sub.4OC.sub.2 H.sub.5                                                           ##STR119## 2 1 1                           H         C.sub.3 H.sub.6COOH                                                                         ##STR120##                                                                               ##STR121## 2 1 1                           H         C.sub.6 H.sub.13                                                                           H                                                                                         ##STR122## 2 1 1                           H         C.sub.9 H.sub.19                                                                           H                                                                                         ##STR123## 2 1 1                           H         C.sub.15 H.sub.31                                                                          C.sub.4 H.sub.9                                                                           ##STR124## 2 1 1                           H         C.sub.20 H.sub.41                                                                          H                                                                                         ##STR125## 2 1 1                           H         C.sub.4 H.sub.9                                                                            H                                                                                         ##STR126## 2 1 1                           H         C.sub.3 H.sub.7                                                                            H                                                                                         ##STR127## 2 1 1                           H         C.sub.2 H.sub.5                                                                            H                                                                                         ##STR128## 2 1 1                           CH.sub.3  C.sub.2 H.sub.5                                                                            H                                                                                         ##STR129## 2 1 1                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                            CH.sub.3                                                                                  ##STR130## 2 1 1                           C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                                                            CH.sub.2SO.sub.3 H                                                                        ##STR131## 2 1 1                           C.sub.2 H.sub.4 Br                                                                      C.sub.2 H.sub.5                                                                            CH.sub.2SO.sub.3 H                                                                        ##STR132## 2 1 1                           C.sub.2 H.sub.4OCH.sub.3                                                                C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2COOH                                                                     ##STR133## 2 1 1                           C.sub.2 H.sub.4SO.sub.3 H                                                               C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2COOH                                                                     ##STR134## 2 1 1                           C.sub.4H.sub.8COOH                                                                      C.sub.2 H.sub.5                                                                            CH.sub.3                                                                                  ##STR135## 2 1 1                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                                                                            CH.sub.3                                                                                  ##STR136## 2 1 1                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                         CH.sub.3                                                                                  ##STR137## 2 1 1                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                         H                                                                                         ##STR138## 1 1 1                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                         H                                                                                         ##STR139## 1 1 1                           H         C.sub.2 H.sub.4SO.sub.3 H                                                                  H                                                                                         ##STR140## 1 2 1                           H         C.sub.2 H.sub.4SO.sub.3 H                                                                  H                                                                                         ##STR141## 1 1 1                           H         C.sub.2 H.sub.4 OH                                                                         H                                                                                         ##STR142## 1 2 1                                                  H                                                                                         ##STR143## 0 0 3                                                  C.sub.2 H.sub.5                                                                           ##STR144## 1 0 2                           H         CH.sub.2COOH H                                                                                         ##STR145## 1 1 2                                                  H                                                                                         ##STR146## 1 0 3                                                  H                                                                                         ##STR147## 0 0 4                                                  H                                                                                         ##STR148## 1 0 1                           __________________________________________________________________________

EXAMPLE 4

The diazonium compound that supplies the fiber-reactive group in Example1, that is to say the cyanurylated metaphenylene diamine-sulphonic acid,is replaced by an equivalent amount of diazotized2-amino-4-acetylamino-benzenesulphonic acid and the procedure followedis otherwise as described in Example 1.

200 ml of 10 N sodium hydroxide solution are subsequently added to thesolution of the green azo phthalocyanine dye formed and the mixture isstirred for five hours at 95° until the acetyl group is completelysaponified.

The dye solution thus obtained is neutralised with about 100 ml of 10 Nhydrochloric acid and a solution of 190 g of cyanuric chloride inacetone is then added at 0°-5° C. The pH value is simultaneously keptbetween 5.0 and 6.5 by adding about 80 g of sodium bicarbonate inportions. The reaction has ended when no further amino groups which canbe diazotised can be detected.

The fiber-reactive dye thus obtained is identical to that manufacturedaccording to Example 1.

EXAMPLE 5

188 g of m-phenylenediamine-sulphonic acid are dissolved in about 6,000ml of water to give a neutral solution. 190 g of cyanuric chloride,dissolved in acetone, are added to this solution at 0°-5° C. and the pHis simultaneously kept between 6 and 7 with about 100 ml of 10 N sodiumhydroxide solution. When no further m-phenylenediamine-sulphonic acidcan be detected, 70 g of sodium nitrite are added to the neutralsolution and the mixture is then stirred into 250 ml of 10 Nhydrochloric acid at 0°-3° C. When the diazotisation ceases, the diazosuspension is added to a solution ofN-[3-(3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho-phenyl]-Ni-trisulpho-phthalocyaninylsulphonamide,to which 100 g of bicarbonate have previously been added. The couplingceases in a few minutes.

The green reactive phthalocyanine azo dye thus obtained has two labilechlorine substituents in the reactive moiety which has the formula##STR149##

It can be modified by the following operation:

173 g aniline-4-sulfonic acid are dissolved in a mixture of 500 ml ofwater and 130 ml of 30% by weight of sodium hydroxide solution. Theresulting solution is added to the green dyestuff solution and themixture is then warmed, in each case for one hour, to 30° C., 40° C. and50° C., the pH being kept between 4 and 7 by adding alkali, such assodium hydrogencarbonate, sodium carbonate or sodium hydroxide solution.

The reactive moiety of the resulting dye has the formula ##STR150## Ithas one labile chlorine substituent and one non-labile aminesubstituent.

The dye can be isolated by salting out or spray-drying. It has a veryhigh degree of fixation on cellulose material particularly if fixing isperformed by means of dry heat. The green dyeings have excellentfastness properties particularly to light, to washing at 60° C. and 95°C. and to perspiration.

If one mol of one of the following compounds is substituted for theaqueous solution of aniline-4-sulfonic acid used in this example,valuable green reactive dyestuffs are likewise obtained. In the case ofammonia or aliphatic amines, the alkali can be replaced by a second molof amine. Ammonia, methylamine, diethylamine, isopropylamine,ethanolamine, diethanolamine, N,N-dimethylhydrazine, aniline, o-, m- orp-toluidine, N-methylaniline, aniline-2- or aniline-3-, sulphonic acid,2-, 3- or 4-aminobenzoic acid, aniline-methanesulphonic acid,β-amino-ethanesulphonic acid, N-methyltaurine, aminoacetic acid,aniline-2,4- or aniline-2,5-disulphonic acid or the condensation productof: p-phenylenediamine, cyanuric chloride and aniline-3-sulphonic acid,ethylene diamine, cyanuric chloride and aniline-2,4-disulphonic acid,1,4-phenylenediamine-2,5-disulphonic acid andiso-propoxydichlorotriazine, 1-3-phenylenediamine-4-sulphonic acid andβ-ethoxyethoxydichlorotriazine, p-phenylenediaminesulphonic acid andcyanuric chloride, p-phenylenediaminesulphonic acid andtetrachloropyrimidine, p-phenylenediaminesulphonic acid and2,3-dichloroquinoxaline-carboxylic acid chloride,p-phenylenediaminesulphonic acid and 2,6-dichloropyrimidine-4-carboxylicacid chloride or p-phenylenediaminesulphonic acid and3,6-dichloropyridazine-4-carboxylic acid chloride.

EXAMPLE 6

281 g of 4-aminophenyl-β-sulphatoethyl sulphone are dissolved in about6,000 ml of water to form a neutral solution. 70 g of sodium nitrite areadded to the neutral solution and the mixture is then stirred into 250ml of 10 N hydrochloric acid at 0°-3° C. When the diazotisation iscomplete, the diazo suspension is added to a solution ofN-[3'-(3-carboxy-5-hydroxy-1-pyrazolyl)-4'-sulpho-phenyl]-Ni-trisulpho-phthalocyaninylsulphonamideto which 100 g of sodium bicarbonate have previously been added. Thecoupling is complete within a few minutes.

The resulting green phthalocyanine azo dyestuff can be isolated bysalting-out or spray-drying. It has the following structure: ##STR151##The solution of the phthalocyanine-pyrazolone which is required for thecoupling can be obtained in the following manner: 1,060 g of3-(3-amino-4-sulpho-phenyl)-amino-sulphonyl-nickel-phthalocyanine-3',3",3"'-trisulphonicacid, which has been prepared in the customary manner by a condensationreaction of nickel phthalocyanine sulphochloride with1,3-diaminobenzene-4-sulphonic acid, are stirred with 7,000 ml of waterand are dissolved by adding 400 ml of 10 N sodium hydroxide solution. 72g of sodium nitrite are added to this solution and the mixture is thenstirred into a mixture of 2,000 g of ice and 300 ml of concentratedhydrochloric acid in the course of 30 minutes. A temperature of 0° to 5°C. is maintained by adding a further 2,000 g of ice. After a short timeany excess of nitrite which may be present is destroyed by addingaminosulphonic acid. 21 g of acetylsuccinic acid dimethyl ester arepoured into the diazo suspension obtained in this way. The pH value isthen kept, first at 5.5 by sprinkling in approximately 13 g of sodiumcarbonate, and then at 5 to 6 using approximately 21 g of sodiumbicarbonate. Stirring is then continued for approximately 1 hour. Theend of the reaction is recognised from the fact that the pH remainsconstant and that no alteration in colour shade occurs when a sample istreated with a solution of H acid in 2 N sodium carbonate.

350 ml of 10 N alkali metal hydroxide solution are added to the solutionof oxalacetic acid dimethyl ester-3-(nickel-trisulpho-phthalocyaninylsulphonylamino)-6-sulphophenylhydrazoneobtained in this way, as a result of which the pH rises to values of 12to 13. The mixture is stirred for a few hours, best overnight at roomtemperature. The rearrangement to giveN-[3-(3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho-phenyl]-nickel-trisulpho-phthalocyaninyl-sulphonamideis then complete; the pH is reduced to 8 with a little hydrochloric acidand the resulting crude solution is employed direct for coupling.

Dyestuffs having similar properties are obtained if, instead of4-aminophenyl-β-sulphatoethyl sulphone, equivalent quantities of thefollowing amines are used: 3-aminophenyl-β-sulphatoethyl sulphone,3-amino-4-methoxyphenyl-β-sulphatoethyl sulphone,4-amino-3-methoxyphenyl-β-sulphatoethyl sulphone,3-amino-4-methylphenyl-β-sulphatoethyl sulphone,3-amino-4-sulphophenyl-β-sulphatoethyl sulphone,4-amino-3-bromophenyl-β-sulphatoethyl sulphone,4-amino-3,5-dichlorophenyl-β-sulphatoethyl sulphone,3-amino-4-carboxyphenyl-β-sulphatoethyl sulphone,3-amino-4-hydroxyphenyl-β-sulphatoethyl sulphone,4-amino-3-hydroxyphenyl-β-sulphatoethyl sulphone,4-amino-2,5-dimethoxyphenyl-β-sulphatoethyl sulphone,4-amino-2-methyl-5-methoxyphenyl-β-sulphatoethyl sulphone,4-aminophenyl-β-(N,N-dimethylamino)-ethyl sulphone,4-aminophenyl-β-(N,N-diethylamino)-ethyl sulphone,4-aminophenyl-β-phosphatoethyl sulphone,4-aminophenyl-β-thiosulphatoethyl sulphone, 4-aminophenyl-β-chloroethylsulphone, 3-aminophenyl-β-chloroethyl sulphone, 4-aminophenyl-vinylsulphone, 4-amino-3-chloro-5-methylphenyl-β-sulphatoethyl sulphone,3-aminobenzyl-β-sulphatoethyl sulphone,β-(4-aminophenyl)-ethyl-β-sulphatoethyl sulphone,3-nitro-4-(4'-aminophenyl)-aminophenyl-β-sulphatoethyl sulphone,2-phenylamino-5-amino-phenyl-β-sulphatoethyl sulphone,4-(4'-aminophenylsulphonyl)-phenyl-β-sulphatoethyl sulphone,3-(4'-aminobenzyl)-amino-phenyl-β-sulphatoethyl sulphone,3-(3'-aminophenylsulphonyl)-aminophenyl-β-sulphatoethyl sulphone,4-amino-1-naphthyl-β -sulphatoethyl sulphone,5-amino-1-naphthyl-β-sulphatoethyl sulphone,6-amino-1-naphthyl-β-sulphatoethyl sulphone,6-amino-2-naphthyl-β-sulphatoethyl sulphone,6-amino-1-sulpho-2-naphthyl-β-sulphatoethyl sulphone,8-amino-2-naphthyl-β-sulphatoethyl sulphone and8-amino-6-sulpho-2-naphthyl-β-sulphatoethyl sulphone.

Valuable green reactive dyestuffs are also obtained if the condensationproduct of nickel phthalocyanine sulphochloride and one of the aminesmentioned in the following text is used for the preparation of thecoupling component instead of the abovementioned condensation product ofnickel phthalocyanine sulphochloride and 1,3-diaminobenzenesulphonicacid, and if the procedure followed is in other respects as described:1,4-phenylenediamine-2-sulphonic acid,1,3-phenylenediamine-4,6-disulphonic acid,1,4-phenylenediamine-2,5-disulphonic acid,1,4-phenylenediamine-2,6-disulphonic acid,2,4-diaminotoluene-6-sulphonic acid, 2,6-diaminotoluene-4-sulphonicacid, 2,4-diamino-1,3,5-trimethylbenzene-6-sulphonic acid,2,6-diaminonaphthalene-4,8-disulphonic acid,1,5-diaminonaphthalene-2-sulphonic acid,2,6-diaminonaphthalene-8-sulphonic acid,1-amino-4-aminomethyl-benzene-3-sulphonic acid,2-amino-5-aminomethyl-naphthalene-1-sulphonic acid,4,4'-diamino-diphenylamine-3-sulphonic acid,3,3'-diamino-4-methyl-diphenyl-sulphone-5-sulphonic acid,1,3-phenylenediamine (acetyl derivative, subsequently saponified),2,4-diaminotoluene (acetyl derivative, subsequently saponified),1,4-phenylenediamine (acetyl derivative, subsequently saponified),4,4'-diamino-diphenylethane-2,2'-disulphonic acid,4,4'-diamino-diphenylethane-mono-sulphamide,4,4'-diamino-diphenylethane-disulphamide,4,4'-diaminostilbene-2,2'-disulphonic acid,4,4'-diamino-diphenylamine-3-sulphonic acid,3,4'-diamino-6-methoxy-diphenylamine-2'-sulphonic acid,3,4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid,3,3'-diaminobenzophenone-5,5'-disulphonic acid,3,4'-diaminobenzophenone-3'-sulphonic acid, 4,4'-diamino-diphenylsulphone, 4,4'-dichloro-3,3'-diamino-diphenyl sulphone,3,3'-diamino-4-methyl-diphenyl-sulphone-5-sulphonic acid and3,3'-diaminodiphenyl-sulphone-4,4'-disulphonic acid.

EXAMPLE 7

281 g of 4-aminophenyl-β-sulphatoethyl sulphone are dissolved in about6,000 ml of water to give a neutral solution. After adding 70 g ofsodium nitrite, the solution is run into 250 ml of 10 N hydrochloricacid and the diazo suspension obtained in this way is then added, asdescribed in Example 1, to a solution of the bispyrazolone prepared asdescribed further on in the text from 535 g of3,3'-bis-[(4-aminophenyl)-amino-sulphonyl]-nickel-phthalocyanine-3",3"'-disulphonicacid. The pH is then adjusted with 4 N sodium carbonate solution to7-7.2 and the green dyestuff which has formed is isolated by salting-outor spray-drying. The dyestuff has the following structure: ##STR152##The bispyrazolone employed as the coupling component was prepared in thefollowing manner: 535 g of3,3'-bis-[(4-aminophenyl)-amino-sulphonyl]-nickel-phthalocyanine-3",3"'-disulphonicacid, prepared in the customary manner by a condensation reactionbetween 0.5 mol of nickel phthalocyanine tetrasulphochloride and 1 molof acetyl-p-phenylenediamine and saponification of the condensationproduct, are stirred with 3,500 ml of water and are dissolved by adding200 ml of 10 N sodium hydroxide solution. 70 g of sodium nitrite areadded to this solution and the mixture is then stirred into a mixture of2,000 g of ice and 300 ml of concentrated HCl in the course of about 30minutes. The temperature is kept between 0° and 5° C. by adding afurther 100 g of ice. Stirring is continued for about 10 minutes and anyslight excess of nitrite which may be present is then removed by meansof amidosulphonic acid. 135 g of acetylsuccinic acid diethyl ester areadded to the diazo suspension obtained in this way. The pH is adjustedto about 6 with approximately 250 g of sodium carbonate and is kept atthis value until the diazo compound can no longer be detected. Thisgives a solution of the turquoise-coloured3,3'-bis-[4-(1,2-bis-ethoxycarbonylethylidene)-hydrazino-phenyl-aminosulphonyl]-nickel-phthalocyanine-3",3"'-disulphonicacid, which is converted direct, by the action of alkali, into thecorresponding bispyrazolone, by adding about 400 ml of 10 N sodiumhydroxide solution to the mixture and stirring for approximately 4 hoursat room temperature.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is, therefore, to beunderstood that within the scope of the appended claims the inventionmay be practiced otherwise than as specifically described.

What is claimed is:
 1. A process of preparing a water-solublefiber-reactive phthalocyanine azo dye in which the phthalocyaninenucleus carries at least one group having the structure ##STR153## whereR is hydrogen or alkyl having up to 6 carbons, andar is a carbocylicdivalent aromatic or araliphatic group containing up to two benzenerings and up to 16 carbons, a benzene ring carrying the nitrogen of theheterocycle and R³ is hydrogen or hydrocarbyl having up to 18 carbonstheprocess comprising reacting a water-soluble phthalocyanine dye in whichthe nucleus has a sulphonyl halide group with an ar-diamine to form a##STR154## product, diazotizing said product and coupling the diazoniumcompound with a aryl-succinic acid ester to yield the configuration##STR155## where R¹ is hydrocarbyl having up to 18 carbons, and R² ishydrocarbyl having up to 18 carbons, and then cyclizing at sufficientlyhigh pH that configuration to the desired pyrazolone structure##STR156## followed by coupling the pyrazolone ring with anotherdiazonium compound carrying the fiber-reactive group.
 2. The process ofclaim 1 in which the sulfonyl halide group is --SO₂ Cl.
 3. The processof claim 1 in which the ketosuccinic acid ester is an acetyl succinicacid ester.
 4. The process of claim 1 in which the phthalocyaninenucleus is a nickel-phthalocyanine nucleus.
 5. The process of claim 1 inwhich the sulfonyl halide groups are in the 3-position of the nucleus.6. The process according to claim 1 wherein cyclizing to produce thedesired pyrazolone is conducted at a pH of about 8-14.
 7. The processaccording to claim 1 wherein cyclizing to produce the desired pyrazoloneis conducted at a pH of about 10-14 whereby R³ becomes H.